Manufacture of phosphorus and compounds thereof



Jan. 12, 1932. w. H. WAGGAMAN ET AL MANUFACTURE OF PHOSPHORUS AND COMPOUNDS THEREOF Filed Dec. 2l, 1925 NN. Q

Patented Jan. 12, 1932 WILLAM E.. VAGGAMAN AND HENBY- W. EASTER-VJOGD, OF CHICAGO HEIGHTS,

ILLNOIS, ASSIGNORS '13() VICTOR CHEMICL vitfls, .A CORPORATIQN OF LLIN 01S IL'ANUFACTURE OF PHOSPHORUS .A1-TB COMPOUNDS THEREOF Application filed December The present invention relates to improvements inthe manufacture of phosphorus or `of compounds thereof, and will be fully understood from the following description, illustrated'by the accompanying drawings, in which:

Figure 1 is a diagrammatic view, Jartiallv in section, showing apparatus suitable for use in carrying outy the present invention; and

2 isa diagrammatic sectional view of condensing apparatus suitable for use in connection with the present invention, as hereinafter set forth.

naccordance With the present invention, the production of phosphorus and compounds thereof fromphosphatic materials is facilitated and the eifective recovery thereof substantially increased.. In the preferred method of carrying out the invention, conditions maybe so maintained that an effective recovery of phosphorus is secured Without the disadvantage of bringing the reaction materials to the fusion point of the mixture.

Tieferring more particularly to the drawings, the numeral 5 indicates an oven or furnace of the by-product coke oven type, that portion on the left of the vertical line ill-.A being shown in section through the retort or muffe-e chamber of a bench, and that portion of the right of theL line A-i being a sectional vieiv through the heating flues interposed betvveenmuffles or retorts in the bench. rlie retort shown may be regarded as one in a bench of retorts, certain of which are employed in the manufacture ofy by-product coke in the usual manner, that illustr: ted Jeing employed in association therewith for the manufactureA of phosphorus or phosphorus compounds as hereinafter more fully set forth.

' The retort or inutile chamber 6 is charged with the nhosphatic reaction min ure by the method usual in charging colte ovens coke; thatl is, the reaction mixture is chai thereinto through the ports 7 from suitable hopper cars 8. The individual retorts or ovens of the bench, which are relatively narrow, are heated in the customary manner, by means of a suitable fuel gas supplied through 21, 1925. Serial No. 76,689.

UDS

ic flues from the regenerators 12, the op- 'ati'on of which is not here described, as it that conventional in coke oven practice.

l-.e retorts 6 are provded vith discharge iipes 15, through which the phosphorus vapors given off by the charge pass out to be handled as he iuafter more fully described. i suitable ram 14 is provided for forcing the spent charge from the retort after completion of the reaction.

In carrying out the invention, the phosphatic charge is prepared for the retorts by admiring previously ground phosphate rock and bituminous coal, both being preferably ground so that 90% thereof will pass through a Ll0 mesh screen. The mixture is so made (Withthe addition of suitable quantities of sand, if required) that the resulting charge has approximately7 he following constitution.

Silica (Si02) 18 to 20%.

(CaO) 34 to 37%.

phosphoric acid (P205) 22 to 25%.

Bituminous coal 18 to 25%.

This mixture is then employed as the charge in the retorts 6. Before charging thismiizture` into the retorts, it is preferred that a small quantity of bituminous coal be charged thereinto toform a layer extending Vover the base or .bottom of the oven, the phosphatic charge being then filled in over this laver of bituminous coal.

The ovens having been charged, they are brought to a temperature between 1100o and 11150o C., at vvhich temperature the reaction takes place and phosphorus is evolved. The charge of the proportions hereinbefore set forth is not reduced to a molten condition, nor does it do more than sinter at temperatures as high as 1450O C. The phosphorus is therefore evolved under these conditions Without fusion of the reaction mixture. The relatively narrow width of the retorts or ovens permits of a very even distribution of heat through the charge.

In accordance with this invention, bituminous coal is employed as the carbonaceous reheated air for combustion is supplied to'l constituents of the charge, and as a result of its use there isa shrinkage of the charge during reaction which substantially facilitates the removal of the spent charge from the furnaces. v The employment of abottom layer of bituminous coal in the retorts, as above i, described, aids substantially in preventing fue 'fill treatment.

adhesion of the charge thereto. Although it is preferred touse this bottom layer of bituminous coal, it may be omittedif desired, the proportion ofbiturninous coal in the charge and the resulting shrinkage reducing substantially the adherence of the charge to the Walls of the oven. During reaction, a suitable non-oxidizing gas, such as nitrogen, carbon monoxide or colle-oven gas may be caused to passV through the retorts, thus aiding in sweeping out the phosphorus vapors. rlhus, in the apparatus herein described,l coke-oven gas derived from other ovens of the bench -maybe supplied through the main 25 and the pipe 26 to the interior of thev retorts 6 in Which the phosphatic charge undergoes A current of the non-oxidizing gas thus supplied is preferably passed through the reaction mixture during Vthe entire period of evolution of phosphorus therefrom. f

' The phosphorus vapors, together With the non-oxidizing gas When the latter is employed, pass out through the pipes 15 into the discharge main 16. If phosphorus is desired as the iinal'product, the vapors are caused to pass from the main 16 through the vvalve controlled line 17 to the condensing apparatus illustrateddiagrammatically in Fig. 2.V If'itis desired to oxidize the vphosphorus vapors to form yphosphorus pentoxid and V'plied to effect the desired oxidization. The

resulting gases. includingphosphorus pentoxid and phosphoric acid. pass into a collecting chamber 20, being suitably forced thereinto by a pump 21. Loss of phosphorus pentthe phosphates.

ers 27, each provided with a condensing Water spray 28 and opening at its bottom below the Water level in a collector 29. The latter has lected phosphorus may be readily Withdrawn therefrom.

Although the present invention has been described in connection With particular details of apparatus and of a method for carrying itinto effect, it is not intended that these details shall be regarded as limitations upon the scope of the invention, except insofar as included in the accompanying claims.

AWe claim: Y

1. The method of producing phosphorus from a phosphatic material Which comprises preliminarily applying to an interior Wall of an externally heated chamber a layer of bituminous coal, subsequently charging the chamber With a phosphatic material admixed lvvith silica and a carbonaceous material, and

applying heat to remove the phosphorus from the charge, adherence of the charge to the Wall of the chamber being thereby prevented.

2. The Vmethod of producing phosphorus which comprises heating in an externally fired chamber to a temperature between 1100o and 1450o a mixture of natural phosphate, silicious material and bituminous coal, the proportion of bituminous coal being in excess of 18% andl that of silica not being above 20%.

3. The method of producing phosphorus from a phosphatic material Which comprises preliminarily applying to an interior Wall of an externally heated chamber a layer of bituininous coal, subsequently charging the chamber with a phosphaticmaterial admixed With silica and a carbonaceous material, and applying sufficient heat to remove the phosphorus from the charge Without fusing said charge, adherence of the charge to the Wall of the chamber being thereby prevented.

4.-. The method of producing phosphorus yfrom a phosphatic material which comprises preliminarily applying to an interior Wall of an externally heated chamber a layer of bituminous coal, subsequently charging the chamber With a phosphatic material admixed Withl silica and bituminous coal, and applying sufficient heat to remove the phosphorus from the charge Without fusing said charge,

Yadherence of the charge to the Wall 'of the chamber being thereby prevented.

QThe method of producing phosphorus Which comprises heating a phosphatic reaction mixture comprising a natural phosphate, silica and carbonaceous material in a chamber. separatelyand simultaneously heating a Coking coal to a colring temperature, thereby evolving coalgas therefronnand Vdrawing said coal gas through .the heated phosphatic reaction mixture.

llLLlAM H. WAGGAMAN. HENRY W. EASTEBW OOD.

a properly drained bottom, so that the col- 

